Structural and mechanistic studies of co-ordination compounds. Part 25. Synthesis and characterization of some octahedral halogeno-amine and -thioether complexes of ruthenium-(II) and -(III)

Abstract

The published methods for the syntheses of trans-[RuLCl₂]⁺[L = L¹, bis(ethane-1,2-diamine); L⁴, 3,7-diazanonane-1,9-diamine; or L⁷, 1,4,8,11-tetra-azacyclotetradecane] have been modified. The modified method is highly efficient and reproducible and it has been employed to prepare other trans-[RuLCl₂]⁺ complexes [L = L², bis(propane-1,3-diamine); L³, bis(NN′-dimethylethane-1,2-diamine); L⁵, 4,7-diazadecane-1,10-diamine; or L⁶, 4,8-diazaundecane-1,11-diamine]. Other dihalogeno-complexes, trans-[RuLBr₂]⁺(L = L¹, L², L⁴, or L⁷) and trans-[RuLl₂]⁺(L = L¹ or L⁴), have been prepared form their corresponding dichloro-complexes through the reactive ruthenium(II) intermediates. Mixed halogeno-complexes of the type trans-[RuL¹(X)Y]⁺[(X)Y =(Cl) Br, (Cl)l, or (l)Br] have been prepared by metathetical procedures. Meanwhile, some macrocyclic quadridentate thioether complexes trans-[RuLCl₂]·2H₂O (L = L⁸, 1,4,8,11-tetrathiacyclotetradecane; or L⁹, 3,6,10,13-tetrathiabicyclo[13.4.0]nona-1,16,18-triene) and trans-[RuL⁸Cl₂][ClO₄]·H₂O have also been synthesized. All these complexes are low-spin monomeric species. The electronic and i.r. absorption spectra of these complexes are discussed.